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WO2004113224A1 - Appareil reutilisable generateur de gaz - Google Patents

Appareil reutilisable generateur de gaz Download PDF

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Publication number
WO2004113224A1
WO2004113224A1 PCT/US2004/019679 US2004019679W WO2004113224A1 WO 2004113224 A1 WO2004113224 A1 WO 2004113224A1 US 2004019679 W US2004019679 W US 2004019679W WO 2004113224 A1 WO2004113224 A1 WO 2004113224A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactants
ofthe
gas
reactant
gas permeable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2004/019679
Other languages
English (en)
Inventor
John J. Warner
Gary A. O'neill
Richard A. Hamilton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Selective Micro Technologies LLC
Original Assignee
Selective Micro Technologies LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Selective Micro Technologies LLC filed Critical Selective Micro Technologies LLC
Priority to JP2006517457A priority Critical patent/JP2006527658A/ja
Priority to AU2004249770A priority patent/AU2004249770A1/en
Priority to EP04776815A priority patent/EP1648818A1/fr
Publication of WO2004113224A1 publication Critical patent/WO2004113224A1/fr
Priority to US11/302,602 priority patent/US20060120945A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C02F1/763—Devices for the addition of such compounds in gaseous form
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVATION OF FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES; CHEMICAL RIPENING OF FRUIT OR VEGETABLES
    • A23B2/00—Preservation of foods or foodstuffs, in general
    • A23B2/70—Preservation of foods or foodstuffs, in general by treatment with chemicals
    • A23B2/704—Preservation of foods or foodstuffs, in general by treatment with chemicals in the form of gases, e.g. fumigation; Compositions or apparatus therefor
    • A23B2/7045—Details of apparatus for generating or regenerating gases
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16—Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/20—Gaseous substances, e.g. vapours
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J7/00—Apparatus for generating gases
    • B01J7/02—Apparatus for generating gases by wet methods
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/024—Preparation from chlorites or chlorates from chlorites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/48—Sulfur dioxide; Sulfurous acid
    • C01B17/50—Preparation of sulfur dioxide
    • C01B17/501—Preparation of sulfur dioxide by reduction of sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
    • C01B21/36—Nitrogen dioxide (NO2, N2O4)
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/04—Disinfection

Definitions

  • the invention relates generally to apparatus for gas generation. More specifically, the invention relates to reusable apparatus having a resealable opening and for use in gas generation.
  • gas for retarding, controlling, killing or preventing microbiological contamination e.g., bacteria, fungi, viruses, mold spores, algae and protozoa
  • retarding, preventing, or controlling biochemical decomposition controlling respiration, deodorizing and/or retarding and preventing chemotaxis to name a few
  • gases include, but are not limited to, chlorine dioxide, sulfur dioxide, nitrogen dioxide, nitric oxide, nitrous oxide, carbon dioxide, hydrogen sulfide, hydrocyanic acid, and dichlorine monoxide.
  • chlorine dioxide can not be transported commercially as a concentrated gas for its use and instead must be generated at the site where it is used.
  • Transportable devices for generating gas generally operate inefficiently and produce unsatisfactory levels of byproducts or reactants that can remain as a residue and contaminate the surrounding environment.
  • the byproduct chlorite leaves residue on food handling equipment and medical and dental surfaces. Human contact with such residue should be avoided or substantially minimized according to FDA and EPA regulations.
  • Another disadvantage of current techniques is the inability to reuse existing devices, resulting in added expense and waste.
  • the present invention provides a reusable apparatus for the controlled, on-site generation of gases, such as sulfur dioxide and chlorine dioxide.
  • gases such as sulfur dioxide and chlorine dioxide.
  • gas can be produced safely, efficiently and economically.
  • waste can be minimized.
  • the apparatus can minimize or even eliminate the release of any ofthe reactants or byproducts from the apparatus.
  • the present invention provides a reusable apparatus for the generation of a gas, the apparatus including a reactant chamber defined at least in part by a gas permeable material and a resealable opening.
  • the gas permeable material may be substantially impervious to the passage of liquid and/or may allow for the controlled passage of gas.
  • the gas permeable material is formed of a robust material capable of providing structural support
  • the reactant chamber further includes a gas impermeable material.
  • the resealable opening is adapted for closure with a cap, a lid, a clamp, or a zip-lock mechanism.
  • the apparatus includes a supporting element disposed adjacent to at least a portion ofthe chamber.
  • the chamber can include two or more compartments.
  • the apparatus further includes one or more reactants disposed in the chamber.
  • the reactants may be mixed.
  • at least one ofthe reactants is disposed in a sachet; at least one ofthe reactants is disposed in a frangible device; at least one ofthe reactants is a tablet; at least one ofthe reactants is in the form of a gel, a liquid or a powder; and/or at least one ofthe reactants is in the form of a pellet, a ring, or a disc.
  • the apparatus includes a hydrotalcite (e.g., a thermally treated hydrotalcite) disposed in the chamber, h addition, the apparatus may further include a relief valve.
  • a hydrotalcite e.g., a thermally treated hydrotalcite
  • the present invention provides a device for gas generation including a reservoir and any ofthe reusable apparatus disclosed herein.
  • the reservoir may be in fluid communication with the reactant chamber.
  • the reservoir may be a humidifier, a spray bottle, a tank, a cartridge, a bottle, a drum, a storage drum, an air conditioner reservoir, or a conduit.
  • the present invention provides a reusable reactant chamber adapted to receive one or more reactants for the generation of gas, defined at least in part by a gas permeable material and a resealable opening.
  • the present invention provides a method of generating gas
  • a reusable apparatus including a reactant chamber defined at least in part by a gas permeable material and a resealable opening, where one or more reactants are disposed in the chamber; and exposing the one or more reactants to an initiating agent (e.g., water vapor, water or a combination thereof) so as to generate gas.
  • an initiating agent e.g., water vapor, water or a combination thereof
  • At least one ofthe reactants and/or the initiating agent is present in a frangible device.
  • the frangible device may be punctured so as to expose the one or more reactants and/or the initiating agent.
  • the apparatus is exposed to an environment comprising the initiating agent, thereby exposing the one or more reactants to the initiating agent.
  • the apparatus may be submerged in the initiating agent. Alternatively, the apparatus may be partially submerged in the initiating agent.
  • the present invention provides a kit including a reusable reactant chamber defined at least in part by a gas permeable material; and one or more reactants.
  • the present invention provides a refill kit including one or more reactants for use in a reusable reactant chamber and optionally, a means for delivery ofthe one or more reactants to a reusable reactant chamber.
  • Figures 1A-C are perspective views of kits including exemplary reusable apparatus ofthe present invention, and a plurality of reactants.
  • Figure 1A features a zip- lock resealable opening.
  • Figures IB and IC feature reusable apparatus having threaded resealable openings and supporting elements disposed outside and inside the gas permeable material, respectively.
  • Figures 1D-G are side views of exemplary reusable apparatus ofthe present invention, each featuring a reactant chamber ( Figures 1D-E), and a reservoir adapted to receive the reusable reactant chamber ( Figures 1F-G).
  • Figure 1H is a side view of an exemplary reusable apparatus ofthe present invention, featuring multiple layers of gas permeable material.
  • Figure II is a side view of an exemplary reusable apparatus ofthe present invention, formed at least, in part, of a robust gas permeable material.
  • Figure 2 A is a side view of an exemplary reusable apparatus ofthe present invention featuring a reactant chamber having a threaded resealable opening, the mated lid of which is adapted to couple to a reservoir.
  • Figure 2B is a side view of an exemplary apparatus ofthe invention featuring a reactant chamber having a threaded resealable opening, the mated lid of which is adapted to couple to a reservoir.
  • the reactant chamber is partially submerged into liquid contained in a reservoir.
  • Figure 2C is a side view of an exemplary reusable apparatus ofthe present invention featuring a reactant chamber having a threaded resealable opening that is also adapted to couple to a reservoir. As shown, the reactant chamber is submerged into the liquid contained in the reservoir.
  • Figures 3A-3B are side views of exemplary apparatus ofthe invention featuring reactant chambers plumbed into conduits.
  • Figure 4 is a. side view of an exemplary apparatus ofthe invention featuring a reactant chamber having a supporting element and a reservoir.
  • Figure 5 is a side view of an exemplary apparatus ofthe invention featuring a reactant chamber and a supporting element that can be introduced into or connected to a conduit.
  • Figures 6 A and 6B are graphs of chlorine dioxide generation by reusable apparatus constructed as described in Example 1.
  • Figure 7 is a graph of chlorine dioxide generation by a reusable apparatus constructed as described in Example 2.
  • the present invention is generally directed to reusable apparatus for the generation of gas.
  • the invention further contemplates kits that include the reusable apparatus and/or reactant in a variety of forms.
  • the invention provides for devices for gas generation, including a reservoir (e.g., a humidifier or a tank) and the reusable apparatus.
  • the present invention also contemplates methods for use ofthe apparatus and/or kits, including refill kits, for the generation of gas.
  • the present invention relates to apparatus and methods for delivering biocidal-effective amounts of a gas such as chlorine dioxide.
  • the apparatus and methods ofthe present invention achieve delivery of a desired amount of gas, at a desired rate, over a desired time period.
  • the amount, rate and duration of delivery can be manipulated by, e.g., choice of reactant amount, reactant ratio, gas permeable materials, and reactant chamber volume and construction. Such manipulations can be exercised by the artisan using only routine experimentation in view ofthe teachings disclosed herein together with knowledge in the art.
  • exemplary embodiments can be employed to conserve resources and cost by reusing the reactant chamber a plurality of times.
  • a resealable opening allows for replacement of reactant as desired.
  • the resealable opening allows for removal of any contents remaining after reaction, such as sachets or byproducts.
  • Another advantage of particular embodiments is the improved economy of space and packaging materials as refill kits can provide reactants in loose or premeasured form, without the need for delivery, storage and use of new reactant chambers containing reactant after every use. The use of premeasured forms of reactants further allows for the convenient generation of a desired concentration or amount of gas.
  • the reactant chamber is defined at least in part by a gas permeable material, and is closed in the sense that the reactants are substantially retained within the reactant chamber.
  • a "gas permeable material” is a material, typically a planar material such as a sheet or film, including, but not limited to, perforated films, non-perforated films and membranes, that allows for the passage of gas. Suitable gas permeable materials are identified herein.
  • a “robust material” is a gas permeable material that has inherent strength and provides structural support.
  • Suitable robust material for use within the invention includes, but is not limited to, polypropylene hydrophobic tube membrane with a pore size of approximately 0.2 micron sold under the designation ACCUREL® PP N8/2 BP by Membrana GmbH (Wuppertal, Germany).
  • a "resealable opening” is an opening that is capable of being sealed, opened, and resealed at least one time, and preferably multiple times.
  • Sachet refers to a closed receptacle for reactant.
  • the sachet is closed in the sense that the reactants, prior to initiation, are substantially retained within the sachet.
  • Sachets can be constructed of, e.g., gas permeable, dissolvable and/or liquid permeable materials. Sachets can be frangible to allow for puncturing ofthe sachets, resulting in the exposure ofthe reactants contained therein.
  • “Impermeable material,” as used herein, refers to a material that substantially prevents or hinders passage of solids, gases and liquids. As contemplated herein, the impermeable materials do not participate in the generation of gas in that, e.g.
  • Impermeable materials can be constructed from various materials, including, but not limited to, polymeric material, glass, metal, metallized polymeric material and/or coated papers. Suitable materials for impermeable materials are described in greater detail below. As used herein, "barrier" materials are impermeable materials.
  • reactant refers to a reactant or a mixture of reactants that generate gas in the presence of an initiating agent.
  • initiating agent includes, but is not limited to, gaseous or liquid water.
  • moisture in the atmosphere can be used as an initiating agent.
  • dry application for the purposes of this application means at least an application where the apparatus ofthe present invention is not immersed in water or any other liquid.
  • wet application for the purposes ofthe present invention means at least an application where the apparatus ofthe present invention is immersed in water, or other liquid, which can optionally include water.
  • the water in which the apparatus is immersed can be used as the initiating agent.
  • the initiating agent can be included within the apparatus, e.g., contained in a frangible pouch disposed within the apparatus.
  • gas is allowed to enter both the liquid in a reservoir and the enclosed spaces above the reservoir.
  • the gas generating apparatus may be partially submerged in the initiating agent (e.g., water), thereby allowing for initiation of gas generation and escape ofthe gas into both the water and the space above it.
  • the initiating agent e.g., water
  • Such techniques are suitable for a variety of applications in accordance with the invention, including decontamination, for example, ofwater storage tanks.
  • water vapor selective refers to a material that selectively allows permeation ofwater vapor and substantially impedes permeation of liquid water. More preferably, the material excludes permeation of liquid water. Typically, the water vapor selective material is hydrophobic. The skilled practitioner typically refers to water vapor selective material as water impermeable, although water vapor can permeate the material. By contrast, the skilled practitioner refers to materials that allow permeation of liquid water as water permeable. Suitable water vapor selective materials can be made from a variety of materials including, but not limited to, polytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE), and fluorinated ethylene propylene (FEP).
  • PTFE polytetrafluoroethylene
  • PP polypropylene
  • PE polyethylene
  • FEP fluorinated ethylene propylene
  • the present invention is generally directed to reusable apparatus for the generation of a gas, the apparatus including a reactant chamber defined at least in part by a gas permeable material and a resealable opening.
  • Gas Permeable Materials The gas permeable materials ofthe present invention allow, for the passage of gas through the material.
  • the materials can be films, sheets, composites, and the like.
  • the gas permeable material is substantially impervious to liquid. This can be advantageous, e.g., to prevent ingress of liquid initiating agents, such as liquid water, and/or egress of solubilized reactants. It can also be advantageous to retain liquid water or solubilized reactants and byproducts within the reactant chamber such that the reaction efficiency is increased.
  • the gas permeable materials allow for the controlled passage of gas. This can be advantageous because the gas permeable materials can be used to control the rate and efficiency ofthe reaction. This allows for control ofthe duration ofthe reaction, the amount of gas generated, the reduction of byproducts, and the like.
  • Gas permeable materials can include robust materials, water vapor selective materials, perforated materials, membranes, selective transmission materials, composite materials, hydrophilic and/or hydrophobic materials, spun bond materials, expanded polymer structure materials (such as ePTFE sold under the BHA-TEX® tradename by BHA Technologies (Kansas City, MO)), microporous membrane (such as polyethersulfone membrane sold under the Membrana ACCUREL® Micro PES tradename by Membrana GmbH (Wuppertal, Germany)), woven materials, and non- woven materials.
  • expanded polymer structure materials such as ePTFE sold under the BHA-TEX® tradename by BHA Technologies (Kansas City, MO)
  • microporous membrane such as polyethersulfone membrane sold under the Membrana ACCUREL® Micro PES tradename by Membrana GmbH (Wuppertal, Germany)
  • woven materials and non- woven materials.
  • the gas permeable membrane may be or include a robust material.
  • the robust material may be used, for example, when the device may encounter abrasive or rough handling and/or when no support or protective enclosure is practical or desired.
  • the robust material is bound to, adhered to, spun to or otherwise affixed to the gas permeable membrane by techniques well known in the art.
  • the robust material may be a support layer, e.g., that is bound or otherwise fixed or held to the gas permeable membrane, but which does not interfere with the permeability ofthe layer.
  • the robust material may be a web, e.g., to which the gas permeable layer is bound to, adhered to, spun to or otherwise fixed or held.
  • the gas permeable membrane may include a copolymer formed, in whole or in part, of a robust material.
  • the gas permeable membrane is made of a robust material, in whole or in part.
  • the nature ofthe robust material itself e.g. , a cross linked material and/or a material with filler
  • particular features ofthe material e.g., the thickness ofthe layer
  • Suitable water vapor selective material includes, but is not limited to, an approximately 1,550 micron thick polypropylene hydrophobic tube membrane with a pore size of approximately 0.2 micron sold under the designation ACCUREL® PP N8/2 BP by Membrana GmbH (Wuppertal, Germany).
  • a preferred gas permeable material is a water vapor selective material.
  • Water vapor selective material is particularly advantageous because it substantially impedes or excludes the diffusion ofwater soluble species, such as water soluble reactants, additives, and reaction byproducts, out ofthe apparatus.
  • Materials that allow liquid water permeation allow soluble species such as soluble reactants to permeate the apparatus and enter the environment. Prior attempts have been made to ameliorate or avoid escape of soluble species by using insoluble reactants or by binding or otherwise disposing the soluble species on insoluble materials such as clays and molecular sieves, thereby introducing additional steps and/or expense to the preparation ofthe apparatus.
  • the water vapor selective materials ofthe present invention are advantageous because they impede or preclude the permeation ofthe soluble reactants, additives, and byproducts, thus obviating the need to include or generate insoluble reactants, byproducts and/or additives. Water vapor selective materials also are advantageous because their use eliminates the need to use any further materials to retain soluble species in the apparatus, which also introduces additional steps and expense in the construction ofthe apparatus.
  • the water vapor selective material has a thickness between about 2 microns and about 2,000 microns thick (e.g., 750 microns), a pore size between about 0.005 microns and about 10 microns, and a water intrusion pressure between about 20 millibars and about 6,000 millibars.
  • the water vapor selective material is adhered to or otherwise supported by a support layer that allows liquid water to permeate the support layer.
  • the overall thickness of both the water vapor selective material and the support layer is preferably between about 1 mil and 20 mils.
  • water vapor selective materials having a thickness between about 15 microns and about 300 microns thick, a pore size between about 0.01 microns and about 5 microns, and a water intrusion pressure between about 100 millibars and about 2,500 millibars.
  • this layer has a water permeable support layer such that the total thickness of bbth layers is between about 2 mils and about 10 mils.
  • water vapor selective materials having a thickness between about 20 microns and about 200 microns thick, a pore size between about 0.1 micron and about 3 microns (e.g., 0.5 microns), and a water intrusion pressure between about 200 millibars and about 1000 millibars.
  • this layer has a water permeable support layer such that the total thickness of both layers is between about 3 mils and about 8 mils.
  • a thinner layer and/or large porosity is preferred.
  • the thinner and/or more porous the layer the more rapidly water vapor can diffuse into the apparatus and initiate the reaction, and the more rapidly gas can diffuse out ofthe apparatus.
  • Lower porosity generally will result in slower gas generation and higher porosity generally will result in faster gas generation.
  • a thicker material is preferred, such as between about 5 mils and about 20 mils.
  • a relatively smaller surface area ofthe material can be used.
  • a sachet or a reactant chamber can be constructed from a rigid frame constructed from impermeable materials with water vapor selective materials sealing off one or more openings in the rigid frame.
  • pore size ofthe water vapor selective material can be selected to produce the desired release of gas at specific depths ofwater in which the apparatus will be used.
  • a smaller pore size will correspond to deeper operation by increasing the amount of hydraulic water pressure that the membrane will experience while remaining impermeable to liquid water.
  • Water vapor selective materials suitable for use in constructing the apparatus of the present invention preferably have water vapor permeability of between about 500 g/m 2 /24 hrs and about 200,000 g/m 2 /24 hrs (e.g., 2,000 g/m 2 /24 hrs), as determined by JIS L 1099-1985 (Method B), "Testing Methods for Water Vapour Permeability of Clothes," from the Japanese Standards Association.
  • Water vapor selective materials preferably have a resistance to liquid water permeation of at least about 20 millibars as determined by ISO 811-1981 "Textile fabrics - Determination of resistance to water penetration - Hydrostatic pressure test" published by the International Organization for Standardization.
  • the water vapor selective material(s) ofthe present invention can include a support layer to increase the strength ofthe layer, and/or to increase its ability to bond to the other materials used to construct the apparatus.
  • the support layer preferably allows diffusion or passage of initiating agent to the surface ofthe water vapor selective material.
  • the support layer can be spun, perforated or have large pores that allow passage of liquid water and vapor to the surface ofthe water vapor selective material.
  • the support layer can be affixed to the water vapor selective material by any means, e.g., lamination, casting, co-extrusion, and/or adhesive layers.
  • the water vapor selective material can face the interior or exterior ofthe sachet and/or reactant chamber.
  • the support layer itself can be hydrophilic and/or hydrophobic. If hydrophilic, the support layer can be used to attract and deliver liquid water and/or vapor to the surface ofthe water vapor selective material.
  • Suitable support layers include, but are not limited to, polyethylene, polypropylene, nylon, acrylic, fiberglass, and polyester in the form of woven, non-woven, and mesh layers. Preferably, the support layer thickness is between about 1 mil and 25 mils.
  • Suitable water vapor selective materials include the 0.60 pore size, hydrophobic, polypropylene (PP) membrane having a thickness between about 250 microns and about 300 microns sold under the designation 060P1 by Cuno Incorporated (Meriden, CT).
  • hydrophobic polyethylene material sold under the trade designation DOHP by Millipore (Bedford, MA).
  • DOHP 0.65 micron pore size, hydrophobic polyethylene material sold under the trade designation DOHP by Millipore (Bedford, MA).
  • Another water vapor selective material suitable for use in a rapid release apparatus, includes a 1.5 mil thick, hydrophobic polytetrafluoroethylene (PTFE) layer thermally bonded to a 5 mil thick, hydrophobic polyethylene (PE) support layer sold under the trade designation BHA- TEX® by BHA Technologies (Kansas City, MO). Its resistance to liquid water permeation is at least about 500 millibar.
  • PTFE polytetrafluoroethylene
  • PE polyethylene
  • PP polypropylene
  • Membrana GmbH Wuppertal, Germany
  • ACCUREL® PP2E HF about 160 microns thick
  • ACCUREL® PP1E about 93 microns thick
  • the gas permeable membrane includes a perforated material.
  • Perforated materials suitable for use in accordance with the present invention include, but are not limited to, perforated materials having a water vapor transmission rate (WNTR) between about 50 g/m 2 /24 hrs and about 1,000 g/m 2 /24 hrs, between about 200 g/m 2 /24 hrs and about 800 g/m 2 /24 hrs, or between about 400 g/m 2 /24 hrs and about 700 g/m 2 /24 hrs.
  • WNTR water vapor transmission rate
  • the measurement ofwater vapor transmission rate is routine and well known in the art.
  • the perforated material is hydrophobic, in others it is hydrophilic.
  • Exemplary perforated materials include Cryovac® polymeric perforated films available from Sealed Air Corporation (Duncan, SC).
  • One such material is a hydrophobic polypropylene copolymer film sold under the designation SM700 by Sealed Air Corporation that has 330 holes per square inch having a diameter of 0.4 mm, a 6.4% perforated area, a thickness of about 20 microns, and a water vapor transmission rate of 700 g/m 2 /24 hrs.
  • Another suitable film is a hydrophobic polypropylene copolymer material sold under the designation SM60 by Sealed Air Corporation and has 8 holes per square inch having a diameter of 0.4 mm, a 0.2% perforated area and a water vapor transmission rate of 65 g/m 2 /24 hrs.
  • SM60 hydrophobic polypropylene copolymer material sold under the designation SM60 by Sealed Air Corporation and has 8 holes per square inch having a diameter of 0.4 mm, a 0.2% perforated area and a water vapor transmission rate of 65 g/m 2 /24 hrs.
  • the gas permeable membrane for use in accordance with the present invention includes hydrophobic, liquid water permeable materials, such as polyethylene or polypropylene. These materials preferably are between about 1 mil and about 10 mils thick with a water intrusion pressure of about 20 millibars or less.
  • Hydrophobic materials suitable for use as gas permeable materials in accordance with the present invention include, but are not limited to, non-woven polyethylene such as the TYNEK® non-woven polyethylenes from DuPont Company (Wilmington, DE), for example, the TYNEK® 1025D non-woven polyethylene which has an intrusion pressure of less than 20 millibars.
  • membranes are also suitable for use as gas permeable materials.
  • Hydrophilic membranes for example, a pore size between about 0.001 microns and about 50 microns, preferably between about 0.05 microns and 40 microns, and, more preferably, between about 0.1 and about 30 microns.
  • Suitable membranes also include, but are not limited to, the microporous ultra high density polyethylene membrane sold under the trade designation MPLC from Millipore (Bedford, MA), and the microporous Nylon 6,6 membrane sold under the designation 045ZY by Cuno Incorporated (Meriden, CT).
  • Suitable extruded membranes which include cast membranes, include 0.65 micron pore size, 230 to 260 micron thick, hydrophilic polyethylene membrane sold under the trade designation MPLC from Millipore (Bedford, MA), and 0.65 micron pore size, extruded hydrophobic polyethylene material sold under the trade designation DOHP by Millipore (Bedford, MA). Also suitable is the cast membrane 3 micron pore Nylon 6,6 material sold under the trade designation BIODYNE A by Pall (Port Washington, NY).
  • Suitable cast membranes include 0.45 pore, hydrophilic Nylon 6,6 membranes with a polypropylene backbone sold under the designation BA05 by Cuno Incorporated (Meriden, CT); 0.45 pore, hydrophilic polypropylene membrane available from 3M (St. Paul, MN); and 0.45 pore size, 180 to 240 micron thick, hydrophilic Nylon 6,6 membranes sold under the designations 045ZY and 045ZN by Cuno Incorporated (Meriden, CT). Also suitable are hydrophobic, liquid water permeable non-woven polyethylenes, such as the TYNEK® 1025D polyethylene material from DuPont Company (Wilmington, DE).
  • ⁇ on- woven membranes can be formed, e.g., by suspending the membrane material, e.g., cellulose fibers, in a liquid over a porous web and then draining the liquid to form a membrane.
  • ⁇ on-woven membranes typically have a relatively narrower and more consistent pore size distribution as compared to woven materials. Consequently, the material generally allows less initiating agent into the reactant chamber and or sachet than a woven material having the same pore size.
  • a non-woven membrane suitable for use in accordance with the present invention is the 0.65 micron pore size, hydrophobic, non-woven polypropylene material sold under the trade designation A ⁇ O6 by Millipore (Bedford, MA).
  • Pore size affects the rate at which water and ions can diffuse through the material in both directions
  • the pore size ofthe material employed can be chosen to allow entry of initiating agent through the material and, at the same time, retain the reactants within the reactant chamber and/or sachet at a high concentration so that the reaction rate is increased and a high efficiency is maintained.
  • Suitable membranes include those having a pore size between about 0.001 ⁇ and about 50 ⁇ m, between about 0.05 ⁇ m and about 40 ⁇ m, or between about 0.10 ⁇ m and 30 ⁇ m.
  • the pore size ofthe materials also can be measured by bubble point.
  • Bubble point is a measurement well known in the art which approximates pore size from a measurement ofthe pressure necessary to drive a bubble of gas through a wetted membrane.
  • Suitable membranes include those having a bubble point between about 2 psi and about 100 psi, between about 5 psi and about 80 psi, or between about 10 psi and about 70 psi.
  • Suitable membranes also include those having a thickness between about 5 microns and 2,000 microns, more preferably between about 20 microns and 400 microns, and most preferably between about 75 microns and 300 microns.
  • Suitable membranes also include restricted access membranes which include membranes that are liquid water impermeable but restrict the passage ofwater ions and/or solubilized species such as solubilized reactants or byproducts.
  • the gas permeable membrane includes selective transmission materials.
  • Selective transmission materials are neither perforated nor porous, but instead transfer gases through the polymer structure ofthe film.
  • Selective transmission materials are multilayered or mixed polymer materials, where the layers and the polymers are chosen for controlled transmission of gases such as carbon dioxide and oxygen.
  • Selective transmission materials are preferred in dry applications because it allows the gas to diffuse out ofthe reactant chamber or sachet, while retaining the initiating agent once released from a frangible pouch.
  • the selective transmission material increases the stability ofthe apparatus prior to its use because it does not easily allow the ingress of ambient water, which could prematurely initiate the reactants.
  • the selective transmission material has a selective gas transmission rate of between about 500 cc/m 2 /24 hrs and about 30,000 cc/m 2 /24 hrs for CO 2 and between about 1,000 cc/m 2 /24 hrs and about 10,000 cc/m 2 /24 hrs for O 2 .
  • the material has a selective gas transmission rate of between about 1,000 cc/m 2 /24 hrs and about 25,000 cc/m 2 /24 hrs for CO 2 and between about 2,000 cc/m 2 /24 hrs and about 10,000 cc/m 2 /24 hrs for O 2 .
  • the material has a selective gas transmission rate of between about 5,000 cc/m 2 /24 hrs and about 25,000 cc/m 2 /24 hrs for CO 2 and between about 3,000 cc/m 2 /24 hrs and about 10,000 cc/m 2 /24 hrs for O 2 .
  • Measurement of selective gas transmission rate is routine and well known in the art.
  • One suitable selective transmission material is a multilayered polymer film having a carbon dioxide transmission rate of 21 ,000 cc/m 2 /24 hrs and an oxygen transmission rate of 7,000 cc/m 2 /24 hrs sold under the trade designation PD-961 Cryovac® selective transmission film from Sealed Air Corporation (Duncan, SC).
  • gas permeable membranes are woven materials such as materials woven from cotton, metal, polymer threads, metal threads or the like into a cloth or mesh.
  • the gas permeable materials ofthe invention can be constructed employing a material that is hydrophobic and/or hydrophilic. It can include, e.g., a material having one or more hydrophilic zones and one or more hydrophobic zones. These zones can be created, e.g., by chemically attaching, adhering and/or printing a functional chemical group or polymer onto a surface ofthe material that is hydrophilic, hydrophobic or charged to create one or more hydrophilic, hydrophobic or charged zones.
  • a sulfonic acid group can be disposed on the surface ofthe polypropylene membrane, creating zones that are both hydrophilic and negatively charged (R-SO " ).
  • the membrane can then be washed with a dilute acid such that the ion exchange groups (R- SO 2 " ) bind the H + ions.
  • H + ions can later be released to supply H + ions to acid activate reactant, e.g., chlorite, as a replacement or supplement to acid reactant.
  • Such a material can have a hydrophilic surface facing the outside ofthe reactant chamber and a hydrophobic surface facing the interior ofthe reactant chamber.
  • the exterior, hydrophilic surface can aid the initiation ofthe reaction since water will tend to wet the hydrophilic surface.
  • the hydrophobic, interior surface limits water passage out ofthe volume. This keeps the reactants concentrated while allowing the gas to escape thereby exploiting the advantages ofthe discoveries disclosed herein.
  • One such material suitable for use in the present invention is a non-woven membrane with a 0.65 micron pore size diameter formed from a hydrophobic material, such as polypropylene, that has been chemically functionalized with amines and carboxyl groups to produce a charged, hydrophilic surface.
  • the gas permeable membrane may include composite materials, including, but not limited to, starch/polymer composite materials. Suitable composite materials include hydrophilic, 114 ⁇ m thick, non- woven rice starch/polyethylene composites sold under the designation 60MDP-P by Mishima Paper Company, Limited (Japan). This material is heat sealable and wets easily.
  • this material can be used to construct compartment barriers and/or sachets that keep reactants separated until initiation, and/or can be used to control the rate of diffusion of reactants, the rate of gas diffusion, and the initiation ofthe reactant so that the reactant remains concentrated within the reactant chamber and the reaction is driven to completion.
  • the reactant chambers are defined at least in part by a gas permeable material and a resealable opening.
  • the reactant chamber is not necessarily formed entirely ofthe gas permeable membrane.
  • the reactant chamber is formed only in part, of gas permeable membranes, for example, in defined regions of permeability.
  • the reactant chamber may be entirely formed of a gas permeable membrane.
  • the reactant chambers or sachets can include a barrier material and a gas permeable material sealed to each other to define a closed receptacle for reactant. Exemplary embodiments of such apparatus are depicted in the figures. Another example of such a reactant chamber or sachet is a volume defined by a rigid frame defining one or more openings and one or more gas permeable materials disposed about the one or more openings to define a closed receptacle for reactant. Further examples and embodiments are described in greater detail herein, and in the publications incorporated herein by reference. The ratio of reactant chamber volume to reactant volume also can be manipulated to control the concentration ofthe reactants, intermediates, byproducts, etc., within the reactant chamber.
  • the reactant chamber volume is less than about 20 times, 10 times, 6 times, 3 times or 2 times the volume ofthe reactant. In one embodiment, there is no head space such that the ratio is about 1. Smaller ratios are preferred in certain applications. For example, at small ratios, when the reaction produces water, the water increases the pressure inside the volume which, in turn, reduces the rate at which water can diffuse into the reactant chamber. The water to reactant ratio remains constant, thereby allowing the rate of reaction to remain constant. Any method of controlling, fixing or minimizing the void space may be employed in the present invention. By way of example, Figure ID and Figure 4 show a "plug" device that facilitates minimizing the void space enclosed within the reactant chamber.
  • the reactant chamber can include more than one compartment. These sub- compartments of volumes can be defined at least in part by gas permeable and/or impermeable materials. These materials may be used to separate reactants as desired to facilitate the reaction, improve or retard the reaction speed, prevent premature initiation ofthe reaction or otherwise used. For example, a hydrophilic material and or a highly permeable or porous material can be used to facilitate reaction at the interface between two compartments each containing a different reaction, e.g., citric acid and chlorite.
  • a hydrophilic material and or a highly permeable or porous material can be used to facilitate reaction at the interface between two compartments each containing a different reaction, e.g., citric acid and chlorite.
  • the reactant chamber may include suitable impermeable or barrier materials including, but not limited to, metals, glass, polymeric materials and/or coated papers.
  • suitable materials include polymeric layers constructed from, e.g., polyethylene, polypropylene, polyester, styrene, such as polystyrene, polyethylene terephthalate, polyethylene terephthalate glycol (PETG), polyvinyl chloride, polyvinylidene chloride, ethylvinyl alcohol, polyvinyl alcohol, such as polyvinyl alcohol acetate, acrylobutylstyrene and/or polytetrafluoroethylene, polyacrylate and polyamide, such as nylon.
  • polyethylene polypropylene
  • polyester styrene, such as polystyrene, polyethylene terephthalate, polyethylene terephthalate glycol (PETG), polyvinyl chloride, polyvinylidene chloride, ethylvinyl alcohol, polyvinyl
  • metallized layers e.g., any ofthe above polymeric layers that have been metallized.
  • metallic foils such as aluminum foils.
  • Various other impermeable materials can be used to form the barrier film as well, such as glass or ceramics.
  • layers that are composites ofthe above layers and/or laminates ofthe above layers are also suitable.
  • One such material is a 5 mil thick impermeable layer comprising a polyester exterior, a metallized biaxially oriented core, and a polyethylene interior sealing layer available from Sealed Air Corporation (Duncan, SC). This layer has a water vapor transmission rate of 0.01 g/100in /24 hrs at 70% relative humidity and 122°F.
  • Another suitable impermeable material is constructed from polyvinyl chloride.
  • Yet another exemplary material is constructed from polyethylene terephthalate glycol (PETG).
  • the geometry and size ofthe impermeable materials can be adapted to suit various parameters, including the amount and type of reactant to be used, the desired surface area ofthe gas permeable materials, and attachments for the storage and use of the apparatus.
  • the barrier material can be used to form a resealable opening and, optionally, additional portions of a reactant chamber (e.g., a barrier layer can form a cavity to receive reactant in a sachet).
  • the impermeable materials can be formed into various geometries by various manufacturing methods known in the art, including, but not limited to, horizontal form film seal, vertical form fill seal, blister pack, skin pack, injection molding, blow molding, thermoforming, cold forming fill seal, or mechanical forming.
  • the barrier material also may be flexible and not formed into any particular geometry, but sealed about its perimeter to the gas penneable material and other elements ofthe apparatus.
  • the reactant chambers ofthe present invention are defined, in part, by a resealable opening.
  • the resealable opening provides a means for removal and replacement of reactant, thereby allowing for reuse ofthe reactant chamber. Resealing of these volumes can be accomplished, e.g., by a simple adhesive or "zip-lock" mechanism, threaded lids, caps, clamps or similar devices.
  • the resealable opening is constructed from materials substantially impervious to solids, gels, liquids, and gases, at least for the time needed for the reactants to react and produce the gas.
  • a resealable opening, when sealed can be airtight, but is not necessarily so.
  • the resealable opening does not allow a gas generating device (e.g., reactant) to exit when sealed, but does allow exchange of liquid and gas.
  • a pressure relief valve or other device may be employed.
  • Figure IC shows a relief device that allows escape ofthe gas and/or water from the reactant chamber.
  • a pressure relieving technique such as a momentary opening ofthe seal
  • the reusable apparatus ofthe invention may further include a supporting element that can be disposed adjacent to at least a portion ofthe gas permeable material.
  • the supporting element can optionally enclose the reactant chamber in its entirety.
  • the supporting element may be used to facilitate the reaction by sinking or by fixation to specific locations within a vessel containing the initiating agent (water or water vapor in the case of chlorine dioxide).
  • the supporting element may also afford some measure of protection ofthe reactant chamber, including the gas permeable material, and therefore extend the number of times these materials can be reused.
  • the supporting element may have holes, perforations or slots. It may be hydrophilic and or hydrophobic, and/or otherwise facilitate the controlled generation ofthe gas.
  • the present invention provides a gas generation device including a reservoir and the reusable apparatus disclosed herein, hi a particular embodiment, the reservoir is adapted to receive at least a portion of one or more reactant chambers.
  • the reusable apparatus can be affixed, permanently or removably to the device, or may be unaffixed to the device (e.g., the reusable apparatus may float within the reservoir).
  • the reactant chamber is in fluid communication with the reservoir, e.g., it can be disposed partially or fully within the reservoir.
  • the reservoir can be, but is not limited to, a humidifier, a bottle, a spray bottle, a tank, a drum (e.g., a 55 gallon drum), a storage drum, a cartridge, an air conditioner reservoir, a conduit, and or the like.
  • the reservoir can be fitted with one or more devices for introduction and removal ofthe reservoir contents, such as a hose, conduit, spigot, valve or the like.
  • the reusable apparatus includes one or more reactants disposed in the reactant chamber.
  • the reactants may be for the generation of a particular type of gas, for example, chlorine dioxide.
  • Aqueous solutions of a gas (chlorine dioxide, for example) may be generated in situ using methods and devices described in U.S. Patent No. 6,602,466 of Hamilton et al, issued August 5, 2003, U.S. Patent No. 6,607,696 of Hamilton et al, issued August 19, 2003, and U.S. Publication No. 20030053931A1 of Hamilton et al, published March 20, 2003.
  • the reactants can be mixed or separated, e.g., by different reactant chamber compartments and/or sachets.
  • one reactant can be enclosed in a sachet, while the remaining reactants are loose in the reactant chamber.
  • the sachet can include any ofthe gas permeable materials provided herein.
  • the reactant chamber, sachet, or both are constructed with water vapor selective materials.
  • the reactant(s) is incorporated in a sachet thay may be punctured in accordance with the invention, so as to release the reactants in the chamber.
  • the reactants can be in the form of a tablet.
  • the reactants can be in solid, liquid or gel form.
  • the reactants can be in the form of a membrane shell having a wick, as described in International Publication No. WO02/00332.
  • Initiating agent e.g., water
  • Initiating agent e.g., water
  • the reactants can be provided in the form of pellets, rings, disks and any other convenient form.
  • Reactants can be any ofthe reactants and/or reactant mixtures, including additives, described in U.S. Patent No. 6,602,466 of Hamilton et al, issued August 5, 2003, U.S. Patent No. 6,607,696 of Hamilton et al, issued August 19, 2003, and U.S. Publication No. 20030053931A1 of Hamilton et al, published March 20, 2003.
  • the reactants and any additives can be refreshed by opening the resealable opening, inserting fresh reactants and re-sealing the reactant chamber.
  • the new or fresh reactants can be measured amounts of reactants that are provided (1) as separate or mixed reactants in bulk whereby the user measures the appropriate amounts of reactants, (2) as pre-measured packets properly packaged for a desired shelf life which are opened to dispense the measured amounts of reactants, (3) packets enclosed all or in part by barrier, hydrophobic, hydrophilic or dissolvable material or a combination thereof, either as mixed or separate reactants or (4) packets of a bifurcated enclosure comprised all or in part of barrier, hydrophobic, hydrophilic or dissolvable material or combination thereof with each enclosed volume containing one or more reactants.
  • the figures show separated reactants as described above. However, any one or a combination of methods (1) through (4) above may be employed to introduce fresh reactants.
  • multiple packets can facilitate the initiation ofthe reaction, improve contact between reactants and alter the efficiency or speed of the reaction. It also allows the flexibility of allowing generation of desired amounts of gas and or of providing different concentrations of gases in, for example, a reservoir, a chamber, or a room, as desired. For example, more reactant can be used to boost or initially clean a system, address a specific problem, and less reactant can thereafter be used to maintain a desired disinfection level. Instructions and/or charts can be provided that instruct the user how much reactant to add to achieve a desired level of gas and/or for a desired effect.
  • the reactions contemplated by the present invention include the reaction of oxyanions (e.g., carbonates, sulfates, sulf ⁇ tes, chlorates, chlorites, nitrites) and an acid in the presence of liquid water or water vapor.
  • oxyanions e.g., carbonates, sulfates, sulf ⁇ tes, chlorates, chlorites, nitrites
  • the exemplary oxyanions listed in the preceding sentence can also be generally categorized as non-metal oxides, which include the oxides of non-metals (carbon, sulfur, nitrogen, chlorine, etc.).
  • non-metal oxides can be provided in salt form (e.g., with sodium or calcium as the cation) or in anionic form (e.g., in solution).
  • Chlorine dioxide e.g., can be generated by water activation of a mixture of sodium chlorite and an organic acid, such as citric acid. Gas generation can also be accomplished using an aqueous solution of either the acid or the sodium chlorite and initiating the reaction when the solution and the other dry ingredient mix. Other useful gases can also be generated by the initiation of a chemical reaction of dry chemicals by a fluid. Generation of a gas, e.g., by acid activation, is well known in the art. For example, chlorine dioxide (ClO 2 ) is generated from sodium chlorite and an acid, such as citric acid.
  • chlorine dioxide can be produced by the reduction of a chlorate, e.g., sodium chlorate or potassium chlorate, in the presence of an acid, e.g., oxalic acid.
  • a chlorate e.g., sodium chlorate or potassium chlorate
  • an acid e.g., oxalic acid.
  • a sulfite e.g., sodium bisulfite or potassium bisulfite
  • an acid e.g., fumaric acid and/or potassium bitartrate
  • a carbonate e.g., calcium carbonate with an acid, e.g., citric acid
  • nitrite e.g., sodium nitrite or potassium nitrite.
  • gas generation e.g., reduction of chlorates by sulfur dioxide (Mathieson Process)
  • Any acid can be used as a reactant.
  • weak acids are preferred, as they typically are safer to handle, produce less undesirable byproducts, and are less reactive.
  • multiprotic acids are preferred. Multiprotic acids are acids that have more than one reactive site. For example, the triprotic acid, citric acid, is preferred.
  • the aqueous soluble acid is selected from the group consisting of phosphoric acid, fumaric acid, glycolic acid, acetic acid, ascorbic acid, oxalic acid, maleic acid, lactic acid, tartaric acid, citric acid and mixtures thereof. More preferably, the aqueous soluble acid is selected from the group consisting of ascorbic acid, phosphoric acid, oxalic acid, maleic acid, lactic acid, tartaric acid, citric acid and mixtures thereof. Most preferably, the aqueous soluble acid is ascorbic acid, oxalic acid, citric acid and mixtures thereof.
  • the apparatus and methods ofthe present invention are readily applicable to the delivery of more than one gas at one time.
  • the reactant can include both a chlorite and a sulfite for the delivery of both chlorine dioxide and sulfur dioxide.
  • the molar ratio ofthe non-metal oxide salt (e.g., sodium chlorite) to acid is between about 1:0.8 to about 1:5, preferably from about 1:1 to about 1:4, and most preferably from about 1 : 1.15 to about 1:3.
  • additional acid can be added to account for any additives or processing aids such as desiccants, stabilizers, flow agents and the like.
  • a pH between about 1.5 to about 5.5, more preferably a pH of about 3, is maintained by using an excess of acid. Because the reactants are concentrated within the reactant chamber, less acid is needed to drive the reaction to completion and the pH remains low because the acid is concentrated. Furthermore, the reactant salt is consumed by acid and therefore its presence upon completion ofthe reaction is minimized.
  • the reactants can be provided in a kit with one or more reusable apparatus and/or in refill kits for use with reusable apparatus.
  • reusable reactant chambers and/or reusable apparatus ofthe invention can be provided with or without reactants and instructions.
  • Kits can also include instructions for use, test strips for measuring gas concentration, charts that outline the amounts of reactant needed for various applications, and/or devices for measuring reactants.
  • Kits can also include other additives, such as the stabilizers discussed below, flow agents, desiccants, and the like. These additives can be included separately or can be incorporated into the reactant, e.g., in a pellet or a sachet.
  • hydrotalcite may be disposed within the chamber.
  • Hydrotalcite, and the metal hydroxides in the hydrotalcite family can be used to stabilize one or more reactants ofthe present invention.
  • hydrotalcite, including activated hydrotalcite, and metal hydroxides in the hydrotalcite family can be used to stabilize the following reactants and combination of these reactants: acids, aqueous acids, citric acid, oxalic acid, fumaric acid, phosphoric acid, potassium bitartate, chlorites, chlorates, sulfites, bisulfites, sulfates, carbonate, and nitrites.
  • Thermally treated hydrotalcite i.e., hydrotalcite that has been heated to drive off water and or carbon dioxide
  • hydrotalcite that has been heated to drive off water and or carbon dioxide
  • Such apparatus are expected to have a shelf life of at least a year.
  • hydrotalcite The mineral commonly known as hydrotalcite is the naturally occurring form of hydrotalcite, which has the chemical formula: Mg 6 Al 2 (OH) 16 CO 3 -4H O.
  • Hydrotalcite suitable for use in the apparatus ofthe present invention, is commercially available from DIP Chemical Industries (Mumbai, India). When thermally treated, this hydrotalcite is hygroscopic, in that it absorbs water vapor up to about 36% of its weight when exposed to about 97% relative humidity, and has a surface pH between about 11 and about 12.
  • the hydrotalcite can be thermally treated using known methods, e.g., by exposing it to elevated temperatures for an extended period of time, e.g., 500°C for one hour, and thereafter sealing the hydrotalcite in a low humidity environment (including the apparatus ofthe present invention) in order to minimize premature deactivation. Temperatures and times can be varied so as to allow, as desired, more or less water and/or carbon dioxide to be driven off. Such variations are within the scope ofthe invention.
  • the thermal treatment can be exposure to temperatures of 100°C, 200°C, 300°C, 375°C, etc. for 15 minutes, 30 minutes, 2 hours, etc.
  • metal hydroxides in the hydrotalcite family that can be used to stabilize reactants in accordance with the present invention.
  • the family can be described with the general formula: A w B x (OH) y C z -nH 2 O, wherein A is a divalent metal cation, B is a trivalent metal cation, and C is a monovalent, divalent, trivalent, or tetravalent anion.
  • the values for w, x, y, z, and n have the following relationship: 0 ⁇ z ⁇ x ⁇ 4 ⁇ w ⁇ l/2y, and 12 >n >3/2x.
  • Metal cations represented by A include, but are not limited to, Mg , Ni , Fe , and Zn .
  • Metal cations represented by B include, but are not limited to, Al + , Fe + , and Cr 3+ .
  • Chemical species represented by C include, but are not limited to CO 3 " , SO " , OH “ , NO 3 " , and Cf .
  • One such hydrotalcite is a hydrotalcite having the formula: Mg 4 Al 2 (OH) 12 CO 3 -nH 2 O, and is commercially available from Alcoa World Chemicals (Leetsdale, PA).
  • Other suitable minerals in the hydrotalcite family include pyroaurite having the formula Mg 6 Fe 3+ 2 (OH) 16 CO 3 -4H 2 O, and takovite having the formula Ni 6 Al 2 (OH) 16 [(CO 3 )o. 75 (OH)o. 25 ] * 4H 2 O.
  • Hydrotalcite can be added to the reactant such that the resulting mixture is between about 0.5% and about 40% hydrotalcite by weight. More preferably, the resulting mixture is between about 5% and about 20% hydrotalcite by weight.
  • the text hereafter will refer to devices that produce chlorine dioxide with water or water vapor as the initiating agent. One can extend the application ofthe devices to other gases and initiating agents.
  • Figures 1A-1C, 1H, and II depict kits including a plurality of reactant sachets and exemplary reusable apparatus ofthe present invention.
  • Figure 1A depicts a kit including a reactant chamber (15) defined by gas permeable material (20), and including a zipper or "zip-lock” resealable opening (10). Also shown are a plurality of reactants “A” and “B” (30) for insertion into the reactant chamber (15). Reactants (30) can be loose and/or disposed in sachets or other delivery devices.
  • the reactant chamber (15) can be employed a plurality of times by virtue of its "zip-lock” resealable opening (10).
  • the apparatus also features an optional tether (40) attached to the reaction chamber (15) for ease of retrieval from, e.g., a vessel.
  • Figures IB and IC feature kits having reactant chambers (15) defined in part by a gas permeable membrane (20), and having threaded resealabe openings (25) with lids (60) and supporting elements (50, 70) disposed adjacent the gas permeable material (20). Also shown are a plurality of reactants "A" and "B” (30) for insertion into the reactant chamber. Reactants (30) can be loose, compacted (e.g., pellets, disks or the like) and/or disposed within sachets. Supporting elements (50,70) can be employed to protect the membranes (20) either from external stresses or internal stresses. For example, in
  • the supporting element (50) can protect the membrane (20) from puncture by foreign objects and/or can support the membrane (20) when under internal pressure during reaction.
  • supporting element (70) can protect membrane (20) from reactants (30) and other materials (not shown) inserted into the reactant chamber.
  • the supporting member can also be constructed from a material that allows the reactant chamber to sink or float in liquid, depending on the application.
  • Figure IC features a pressure relief device (80).
  • Figures 1D-I are side views of exemplary reusable apparatus ofthe present invention, featuring a reactant chamber ( Figures 1D-E and 1H-I), and a reservoir adapted to receive the reusable apparatus ( Figures 1F-G).
  • Figure ID depicts a reactant chamber (15) including a gas permeable material (20), and a spring-loaded clamp resealable opening (80) that opens wide enough to accommodate the insertion or removal of reactants (30) that are attached to tethers (40) for ease of removal from the reactant chamber.
  • the clamp (80) both secures the tethers and reseals the device. The use ofthe tethers is optional.
  • the threaded top (90) is configured to extend into reservoir (100) shown in Figure IF. This configuration ensures that the reactants remain submerged in any liquid in reservoir (100). Threaded top (90) can be threaded into mated threads (110) in reservoir (100) such that the bottom surface (95) ofthe threaded top (90) defines, in part, a sealed reservoir volume.
  • the reservoir (110) shown in Figure IF can be any container that holds water such as a 55-gallon drum, a 5-gallon pail or a custom-made container.
  • Gas, such as chlorine dioxide can applied using a pump, sprayer, hose or other device inserted into the hole (120) which can be sealed while the chlorine dioxide is generated, and opened to apply the chlorine dioxide solution.
  • Figure IE depicts a reusable apparatus including a reactant chamber (15) defined by a gas permeable material (20) and a lid (130) having a resealable opening (140). Reactants (30) can be placed in the reactant chamber as shown.
  • the apparatus further includes a supporting element or cylindrical container (50) that is permeable to gases and liquids.
  • the supporting element (50) can be constructed of material that supports and/or protects the gas permeable material (20), and/or causes the reactant chamber to sink when inserted into a reservoir (140) as shown in Figure 1G.
  • Reservoir (140) includes a lid (150), which can be employed during generation of gas and or storage of gas solutions. Gas generated can be passed into solution if the reservoir (140) contains a liquid such as water. A removal device such as the spigot (160) can then be used to dispense the solution.
  • Figure 1H depicts another exemplary reusable apparatus.
  • the apparatus is similar to Figure IC, except that Figure 1H features multiple gas permeable membranes (20).
  • Figure II depicts a reusable apparatus having a reactant chamber (15) defined in part by a tubular membrane (21) made of a robust material and having relatively thick walls.
  • the tubular membrane has at least one resealable opening (26) that can be reversibly sealed by a plug (90) or an alternative device, such as a clamp.
  • a plurality of reactants "A" and "B” for insertion into the reactant chamber (15).
  • Figure 2 A is a side view of another exemplary reusable apparatus ofthe present invention featuring a reactant chamber (15) having a threaded resealable opening (25) including a mated lid (60) that is adapted to couple to a reservoir (100).
  • Gas permeable material (20) is enclosed in a permeable supporting element (50) that is attached to the reactant chamber (15) about the resealable opening (25).
  • Reactants (not shown) can be placed in the reactant chamber (15), and inserted into the reservoir (100), to submerge the reactants if sufficient liquid is provided.
  • the resulting solution can be drawn off by means of a metering pump or spigot (160) as shown. Any alternative removal device can be used.
  • Figure 2B is a side view of an exemplary apparatus ofthe invention (similar to that of Figure 2A) showing the reactant chamber (15) partially submerged in liquid within a reservoir (100), thereby allowing gas to escape into both the liquid and the enclosed space above it.
  • Figure 2C is a side view of another exemplary reusable apparatus ofthe present invention featuring a reactant chamber (15) having a threaded resealable opening (25) having a threaded insert (60) that also serves to seal the reservoir (100).
  • the lid (102) attached to the resealable opening (25) extends out over the lip (101) ofthe reservoir (100).
  • the reactants (30) can be refreshed by inserting an assembly of pre-packaged reactants (35) fixed to a holder (not shown) attached to a threaded insert (60).
  • This combination of reactants and threaded insert (60) are screwed into the vessel or reservoir (100) in which the gas permeable material (20) is disposed.
  • the threaded insert (60) has an extended portion (90) that ensures that the reactants are submerged when water fills the vessel (100).
  • an optional spigot (160) and hose (170) Either or both can be used to add and/or remove the contents ofthe reservoir (100). As shown, the reactant chamber is completely submerged in the liquid ofthe reservoir.
  • Figures 3A-B are side views of exemplary apparatus ofthe invention, each featuring a reusable reactant chamber (15), wherein the reactant chamber (15) is positioned in a reservoir (180) that is plumbed into a conduit (75).
  • the reactant chamber (15) in each figure includes gas permeable material (20), and a resealable opening (25).
  • the lid (60) not only defines the reactant chamber but also seals off the cartridge (180).
  • the reactants (37, 30) can be refreshed via the resealable opening (25). Water or other fluids flow through conduit (75) and the cartridge (180) carrying the gas generated and released from the reactant chamber (15).
  • the reactants are in the form of disks (37).
  • the use of disks can be used to facilitate proper placement in the reactant chamber, allow variation in the amount of gas generated (by varying the number of disks inserted), improve contact between reactants, and minimize void space inside the reactant chamber.
  • the reactants (30) are contained in an assembly of pre-packaged reactants (35) fixed to a holder attached to lid or threaded insert (60).
  • Figure 4 is a side view of an exemplary apparatus ofthe invention featuring a reactant chamber (15) defined by the gas permeable material (20), a side wall (18), and a resealable opening (25).
  • the apparatus further includes a supporting element (50), a reservoir (100), and a spigot (160).
  • Gas permeable material (20) is affixed to the wall (18) of a larger vessel or reservoir (100).
  • the boundary wall could be any other boundary wall ofthe reservoir.
  • Resealable opening (25) includes a threaded lid (60) with a plug element (90) to .. ⁇ . ⁇ • ... , _ ⁇
  • lanes defined by polymeric material (e.g., gas permeable, dissolvable, water permeable and/or impermeable materials) where reactants
  • Supporting element (50) can be used to support and/or protect the gas permeable material (20), and/or maintain a specific volume in the reactant chamber (15) as the supporting element (50) can impede the expansion of gas permeable material (20).
  • the contents ofthe reservoir (100) can be drawn off by pump, sprayer, ladle or, as shown, via a spigot (160).
  • Figure 5 is a side view of an exemplary apparatus ofthe invention featuring a reactant chamber (15) and a supporting element (210) adapted to receive it, which supporting element (210) can be introduced into or connected to a conduit (200).
  • the 5 reactant chamber (15) includes a gas permeable material (20), and a resealable opening (25) that includes a lid (60).
  • the reactant chamber (15) and/or the supporting element (210) can be of any convenient shape that may be used to facilitate its use within a conduit and the conduit itself need not be circular in cross-section.
  • the supporting element (210) can be placed or affixed into the conduit (200) and exposed to 0 the initiating agent, e.g., water and/or water vapor.
  • the supporting element (210) is optional, and can be used for a variety of purposes, e.g., to affix the reactant chamber (15) in the conduit (200), to protect the gas permeable material (20), and/or to confine the gas permeable material (20) to the boundary defined 5 by supporting element (210).
  • the supporting element can be constructed from materials formed with open elements or orifices such as perforations, slots, grooves or the like.
  • the supporting element can also have an open structure, such as an open weave or a spun structure.
  • the placement ofthe open elements ofthe supporting element can have 0 directionality in that it controls which portion(s) ofthe supporting element allow the passage of gas and/or liquid.
  • slot can be defined in one area to direct the release of gas from the supporting element into its surrounding environment.
  • the apparatus of Figure 2C can be provided with one or more reactants in a kit, or the apparatus can be sold without the reservoir with and without reactants. Further, the prepackaged reactants of Figure 2C can be provided separately as refill kits.
  • the threaded resealable opening of Figure 2C could be replaced with a valve, clip, etc., and/or the lid attached to the reactant chamber could be otherwise adapted to fit the reservoir, and/or the reactants could be provided in alternative forms with or without additives, such as hydrotalcite, etc.
  • a wide variety of gas permeable materials and sachet embodiments also can be used with the exemplary apparatus depicted in the figures.
  • chlorine dioxide can be used for the disinfection ofwater, e.g., water treatment; as a disinfectant for foods, beverages, fruits and vegetables; and for the cleaning and disinfection of medical, dental and food equipment.
  • Chlorine dioxide has been shown to be an effective disinfectant at concentrations as low as 0.2 mg/1. Chlorine dioxide is a desirable replacement for chlorine, the traditional water treatment chemical, because it has been found to inactivate microbes at lower concentrations and over a wider pH range.
  • chlorine dioxide can be used to reduce or eliminate biofilms and or free floating bacteria because it penetrates the cell wall of naturally occurring, colony-building microorganisms and disrupts the proteins necessary for reproduction.
  • chlorine dioxide does not produce chlorinated byproducts, e.g., trihalomethanes. Moreover, it has been found to be active against pathogens that are resistant to chlorine. It can be used as a slimicide in paper or pulp machines, for wastewater treatment, and for industrial water treatment, e.g., cooling or recycle streams. It can be used for odor control or as an aerial biocide and virucide. It can be used for the treatment of sulfides in the oil industry, for industrial cleaning, e.g., circuit board cleansing, and for paper or tallow bleaching. Sulfur dioxide also has a variety of uses, such as a mold and fungus inhibitor, for example, for use in shipping and storing fruits and vegetables. Based on the teachings disclosed herein, the practitioner of ordinary skill will appreciate the numerous other applications for which the present invention can be used and further provides the solution to a heretofore unmet need.
  • Example 1 Construction and Re-use of a Reusable Apparatus Two reactant chambers were constructed, each 4.62 inches by 3 inches, and formed of Membrana ACCUREL® PP1E hydrophobic membrane sealed about three sides with one side open. Sachets of 3.5 inches by 2 inches, formed of Membrana polyethersulfone ACCUREL® Micro PES 6F hydrophilic membrane, were filled with 7.39 grams of dried citric acid monohydrate and sealed about their perimeter. A mixture of 95% technical sodium chlorite and 5% activated hydrotalcite was prepared.
  • Example 2 Re-Use of a Reusable Apparatus Formed of Robust Material
  • a device of Membrana ACCUREL® PP N8/2 BP hydrophobic tube membrane of 5.5 mm inner diameter with a wall of 1.55 mm thickness and 6.0 cm length was sealed at one end.
  • the device was filled with 279 mg of dried citric acid monohydrate and 185 mg of a mixture consisting of 80% technical sodium chlorite and 20% activated hydrotalcite.
  • the open end was sealed such that the length ofthe tube (not having the seals at both ends) was 4.5 cm long.
  • the filled tube was immersed in 450 ml ofwater.
  • the chorine dioxide generated was measured as chlorine dioxide concentration in the solution surrounding the device. The experiment was repeated three times. The chlorine dioxide generation is depicted in Figure 7.
  • EQUIVALENTS EQUIVALENTS

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Abstract

L'invention concerne un appareil réutilisable conçu pour produire un gaz, qui comporte une chambre de réaction définie, du moins partiellement, par un matériau perméable au gaz et une ouverture refermable. Dans certains modes de réalisation, le matériau perméable au gaz est sensiblement imperméable au passage de liquide et/ou permet le passage régulé du gaz. L'invention concerne également des procédés d'utilisation dudit appareil, des chambres de réaction réutilisables, des trousses comprenant des réactifs et des trousses de recharge de réactifs.
PCT/US2004/019679 2003-06-16 2004-06-16 Appareil reutilisable generateur de gaz Ceased WO2004113224A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2006517457A JP2006527658A (ja) 2003-06-16 2004-06-16 ガス発生のための再利用可能な装置
AU2004249770A AU2004249770A1 (en) 2003-06-16 2004-06-16 Reusable apparatus for gas generation
EP04776815A EP1648818A1 (fr) 2003-06-16 2004-06-16 Appareil reutilisable generateur de gaz
US11/302,602 US20060120945A1 (en) 2003-06-16 2005-12-14 Reusable apparatus for gas generation

Applications Claiming Priority (2)

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US47902903P 2003-06-16 2003-06-16
US60/479,029 2003-06-16

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EP1859814A1 (fr) * 2006-05-24 2007-11-28 The Procter & Gamble Company Système de Déodorisation

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US7789227B2 (en) * 2006-12-28 2010-09-07 Levine Jonathan E Storage and mixing device
US20080241323A1 (en) * 2007-04-02 2008-10-02 Kelsey D Frank Agricultural product disinfecting system
WO2009077213A1 (fr) * 2007-12-19 2009-06-25 Infracor Gmbh Procédé de traitement d'eau avec du dioxyde de chlore
US9044007B2 (en) * 2008-10-08 2015-06-02 Theodore R. Sadler Device and method for ambient storage of fresh/frozen tissue sections via desiccation
DE102008055016A1 (de) 2008-12-19 2010-07-01 Infracor Gmbh Verfahren zur Behandlung von Wasser und wässrigen Systemen in Rohrleitungen mit Chlordioxid
JP2010207539A (ja) * 2009-03-12 2010-09-24 Takasago Thermal Eng Co Ltd 室内処理方法及び処理装置
JP2012111522A (ja) * 2010-11-25 2012-06-14 Pacplus Co Ltd 包装袋
US20130136685A1 (en) 2011-11-25 2013-05-30 Juan Carlos Baselli Portable Chlorie Dioxide Generator
US11279617B2 (en) 2011-11-25 2022-03-22 Juan Carlos Baselli Portable chlorine dioxide generator
US20140199231A1 (en) * 2013-01-12 2014-07-17 Darrel George Wolf System, method and device for generating chlorine dioxide
JP6375098B2 (ja) * 2013-01-24 2018-08-15 高砂熱学工業株式会社 二酸化塩素ガス発生システム、及び二酸化塩素ガス分解装置
CN105579125B (zh) * 2013-09-06 2019-04-19 株式会社M光能源开发研究所 装备疏液性多孔膜的电化学反应器
CN105246492B (zh) * 2014-03-13 2017-09-29 水株式会社 含氢生物体应用液的制造方法、及用于该制造方法的外包装体
JP6322666B2 (ja) * 2016-05-26 2018-05-09 高砂熱学工業株式会社 二酸化塩素ガスの発生装置、容器および二酸化塩素ガスの利用方法
JP7016073B2 (ja) * 2017-04-14 2022-02-04 有限会社 アクアサイエンス 水素発生シャワー
US11129913B2 (en) 2019-07-08 2021-09-28 Odorstar Technology, Llc Disinfectant pouch with fluid control
JP7737662B2 (ja) * 2020-04-13 2025-09-11 パスタライズ株式会社 二酸化塩素発生具
US11672880B2 (en) * 2020-04-20 2023-06-13 Honeywell Federal Manufacturing & Technologies, Llc Methods and devices for sterilizing medical equipment
WO2021222305A1 (fr) * 2020-04-27 2021-11-04 Czap Research And Development, Llc Antisepsie à base de dioxyde de chlore à libération prolongée
JP7562121B2 (ja) * 2020-06-22 2024-10-07 株式会社ルミカ 気体発生装置
US12036525B2 (en) 2020-10-27 2024-07-16 Selective Micro Technologies, Llc Gas micro reactor utilizing membrane packaging
WO2022155599A1 (fr) * 2021-01-15 2022-07-21 Selective Micro Technologies, Llc Insert de bouteille de pulvérisation comprenant un micro-réacteur de production de dioxyde de chlore utilisant un emballage à membrane
JP7730132B2 (ja) * 2021-04-23 2025-08-27 株式会社ルミカ 水溶液の製造装置および水溶液の製造方法

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EP1859815A1 (fr) * 2006-05-24 2007-11-28 The Procter & Gamble Company Procédé de réduction des odeurs mauvaises
EP1859814A1 (fr) * 2006-05-24 2007-11-28 The Procter & Gamble Company Système de Déodorisation
WO2007135653A1 (fr) * 2006-05-24 2007-11-29 The Procter & Gamble Company Procédé destiné à réduire les mauvaises odeurs
WO2007135652A1 (fr) * 2006-05-24 2007-11-29 The Procter & Gamble Company Système de désodorisation

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US20060120945A1 (en) 2006-06-08
EP1648818A1 (fr) 2006-04-26
JP2006527658A (ja) 2006-12-07
CN1809507A (zh) 2006-07-26

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